160 Geothermal Power Plants: Principles, Applications, Case Studies and Environmental Impact

Table 8.2 Thermodynamic properties of some candidate working fluids for binary plants.

Fluid Formula Tc
C Tc
F Pc MPa Pc lbf/in2 Ps @ 300 K MPa Ps @ 400 K MPa

Propane C3H8 96.95 206.5 4.236 614.4 0.9935 n.a.

i-Butane i-C4H10 135.92 276.7 3.685 534.4 0.3727 3.204
n-Butane C4H10 150.8 303.4 3.718 539.2 0.2559 2.488
i-Pentane i-C5H12 187.8 370.1 3.409 494.4 0.09759 1.238
n-Pentane C5H12 193.9 380.9 3.240 469.9 0.07376 1.036
Ammonia NH3 133.65 272.57 11.627 1686.3 1.061 10.3
Water H2O 374.14 705.45 22.089 3203.6 0.003536 0.24559

Fig. 8.8 Temperature-entropy diagram contrasting normal and retrograde saturated vapor curves.

Binary mixtures of these fluids have also been studied for use in geothermal binary
plants. In particular, the thermodynamic properties of 90% i-C4H10 and 10% i-C5H12
were determined by the National Bureau of Standards (predecessor of NIST) in
Washington [10] when it was chosen as the working fluid for the Heber Binary
Demonstration plant in the 1980s; see Chap. 18. Mixtures evaporate and con-
dense at variable temperature, unlike pure fluids that change phase at constant
temperature. This means that subcritical-pressure boilers for mixed fluids can be
better matched to the brine curves, in a manner similar to, but not exactly like,
supercritical pure fluids.
Another important characteristic of binary candidate fluids is the shape of the
saturated vapor curve as viewed in temperature-entropy coordinates; see Fig. 8.8. This
curve for water (shown as the thin line) has a negative slope everywhere, but certain
hydrocarbons and refrigerants show a positive slope for portions of the saturation line.
That is, there exists a local minimum in the entropy at some low temperature, Tm, and
a local maximum in entropy at a higher temperature, TM. Retrograde fluids include
normal butane, isobutane, normal pentane, and isopentane. These fluids exhibit retro-
grade behavior over the following temperature ranges, Tm - TM: C4H10, 23
C - 127
C;
i-C4H10, 23
C - 117
C; C5H12, 23
C - 177
C; i-C5H12, 213
C - 177
C. Since Tm
is lower than any temperatures encountered in geothermal binary plants, for practical
purposes these fluids can be taken as having saturated vapor lines similar to that shown
in Fig. 8.8. This has major implications for Rankine cycles.